Emissions of NOx and SO2 from Coals of Various Ranks, Bagasse

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Emissions of NOx and SO2 from Coals of Various Ranks, Bagasse, and Coal-Bagasse Blends Burning in O2/N2 and O2/CO2 Environments. Feyza Kazanc,† Reza Khatami,† Paula Manoel Crnkovic,‡ and Yiannis A. Levendis*,† † ‡

Mechanical and Industrial Engineering, Northeastern University, Boston, Massachusetts 02115, United States Mechanical Engineering, Escola De Engenharia De S~ao Carlos, University of S~ao Paulo, Brazil ABSTRACT: Oxy-coal combustion is a viable technology, for new and existing coal-fired power plants, as it facilitates carbon capture and, thereby, can mitigate climate change. Pulverized coals of various ranks, biomass, and their blends were burned to assess the evolution of combustion effluent gases, such as NOx, SO2, and CO, under a variety of background gas compositions. The fuels were burned in an electrically heated laboratory drop-tube furnace in O2/N2 and O2/CO2 environments with oxygen mole fractions of 20%, 40%, 60%, 80%, and 100%, at a furnace temperature of 1400 K. The fuel mass flow rate was kept constant in most cases, and combustion was fuel-lean. Results showed that in the case of four coals studied, NOx emissions in O2/CO2 environments were lower than those in O2/N2 environments by amounts that ranged from 19 to 43% at the same oxygen concentration. In the case of bagasse and coal/bagasse blends, the corresponding NOx reductions ranged from 22 to 39%. NOx emissions were found to increase with increasing oxygen mole fraction until ∼50% O2 was reached; thereafter, they monotonically decreased with increasing oxygen concentration. NOx emissions from the various fuels burned did not clearly reflect their nitrogen content (0.2
1.4%), except when large content differences were present. SO2 emissions from all fuels remained largely unaffected by the replacement of the N2 diluent gas with CO2, whereas they typically increased with increasing sulfur content of the fuels (0.07
1.4%) and decreased with increasing calcium content of the fuels (0.28
2.7%). Under the conditions of this work, 20
50% of the fuel-nitrogen was converted to NOx. The amount of fuel-sulfur converted to SO2 varied widely, depending on the fuel and, in the case of the bituminous coal, also depending on the O2 mole fraction. Blending the sub-bituminous coal with bagasse reduced its SO2 yields, whereas blending the bituminous coal with bagasse reduced both its SO2 and NOx yields. CO emissions were generally very low in all cases. The emission trends were interpreted on the basis of separate combustion observations.

’ INTRODUCTION Half of the electricity in the US (40% globally) is generated by electric utilities burning coal. Electric utilities are responsible for 73% of the total US emissions of SO2 as well as 22% of the total US emissions of NOx.1 Nearly all of the utility-generated SO2 emissions and most of the utility-generated NOx (NO, NO2) emissions arise from coal-burning power-plants, as coal contains sulfur and nitrogen in its matrix. NOx and SO2 are regulated atmospheric pollutants.1 Such power-plants are also among the largest point source emitters of the major greenhouse gas: carbon dioxide (CO2). Thus, regulatory pressure is expected in the future to reduce and/or capture and sequester CO2 emissions. Whereas, power generation from CO2-neutral renewable fuels is being promoted, coal utilization is expected to continue in the future, as the reserves of coal are abundant.2 Thus, methods for achieving “clean”-coal combustion are of technological interest. Following coal, petroleum and natural gas, biomass is the next abundant carbon-based energy resource.3 Co-combustion of biomass and coal has generated widespread interest, because of the reduced emissions of gases such as CO2, SO2, and NOx compared to those emitted by the combustion of neat coal. Biomass alone may not be used as a fuel in existing coal-fired furnaces due to its low bulk density, high moisture content, and low energy content.4,5 However, its cofiring with coal is advantageous, based on its higher volatile matter content and its lower pyrolysis temperature, which can aid the ignition and combustion characteristics of the blend.6 Each percentage point of coal replaced by r 2011 American Chemical Society

biomass results in about 60 Mt of CO2 avoided per year globally.7 Co-utilization of biomass also provides an economical and sustainable method for electric power generation.8 Moreover, using waste biomass as a fuel curtails its prolonged storage, which can generate methane (CH4), a potent greenhouse gas. Therefore, on the basis of recognized environmental and economic benefits of using biomass as a fuel,9
13 it has been projected that the biomass share in electricity production may increase from the current 1.3% to some 3
5% by 2050.7 For the reasons discussed above this study incorporated bagasse, which is a waste residue after sugar and/or ethanol have been produced from sugar cane. The largest producers of bagasse are India and Brazil. The sugar cane harvest in Brazil was 570 million tons in 2009. This process generated 190 million tons of bagasse residue, which supplied 3% of the Brazilian energy matrix that year. It is projected that by 2020 this figure will increase to 14%.14 Given the documented increasing concentration of carbon dioxide in the atmosphere, and its likely relation to global warming, several technologies are being developed to facilitate carbon capture and storage (CCS) from fossil-fuel-fired power plants. Among them, oxy-fuel combustion is of technological interest, as it requires the least design and operational departures from Received: March 16, 2011 Revised: May 30, 2011 Published: June 01, 2011 2850

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Energy & Fuels currently practiced combustion techniques. The popularity of oxy-fuel combustion, initially proposed by Horn and Steinber15 and Abraham,16 has increased dramatically in recent years. This technology is capable of providing a CO2 volume fraction in the flue gas of 95% or higher, which is desirable for subsequent sequestration purposes.17 In oxy-combustion, a fuel is burned in an O2
CO2 environment, as opposed to an O2
N2 environment in the case of conventional combustion in air. The differences between air and oxy-fuel combustion are mainly in the properties of CO2 and N2 diluent gases such as density, heat capacity, thermal and molecular diffusivities, and gas emissivity. These properties influence the heat transfer, flammability limits, ignition behavior, and the combustion kinetics of burning pulverized coal.18,19 Oxygen is supplied to the furnace by an air separation unit, and a portion of the flue gas is recycled to moderate the boiler temperature. Upon condensation of H2O, the resulting combustion effluent is mostly CO2, which may be subsequently pressurized and piped to a suitable underground reservoir, in which it is stored. As an additional benefit of this technology, sizable reductions of NOx emissions have been reported.20
22 This work is part of a broader basic investigation to assess the fundamentals of combustion behavior and evolution of gaseous and condensed-phase emissions from coal and biomass, burning in different O2/N2 and O2/CO2 environments. This particular research addresses the evolution of the gas-phase emissions of NOx, SO2, and CO2. While there is not a standard background gas composition for oxy-coal combustion, the most accepted compositions, based on research undertakings and pilot studies, consist of 25
42% O2 mixed with typically dried recycled gases which, in turn, are mostly composed of CO2.23
32 In contrast conventional fired combustion uses air, which is composed of 21% O2
79% N2. In oxy-coal combustion, the nitrogen is replaced by recycled CO2. The oxygen range that was chosen for this study includes the conventional air-fired boiler setting (21% O2), as well as the typical oxy-fuel combustion oxygen range (25
42% O2). The range was then expanded to include even higher oxygen mole fractions (up to 100%), as lowering the flue gas recirculation (if that were feasible given materials considerations) can decrease the size of boilers and reduce the electricity demands of the flue-gas recirculation fans. Four coals of different ranks (bituminous, sub-bituminous, and lignite) were burned. Moreover, sugar cane bagasse (a biomass residue from sugar or bioethanol production) was also burned under similar conditions, either as a neat fuel or blended with coal. In this study, the fuels were burned in an externally heated drop-tube furnace in atmospheres of O2/N2/CO2 gases. Flue gas recycling was simulated by the presence of CO2. Therefore, because actual flue gas recycling was not implemented herein, combustion-generated NOx or SO2 were not returned to the furnace. Thus, the impact of replacing N2 with CO2 was examined without (a) the interfering effects of NO “re-burning” on the final NOx emissions and (b) the effects of extended residence time of SO2 in the furnace and inhibited decomposition of any formed CaSO4 in the ash because of enhanced SO2 concentration in the furnace.33

’ LITERATURE REVIEW Emissions of Nitrogen Oxides (NOx). NOx emissions from burning coal are mostly composed of “thermal-NOx” and “fuelNOx”. The former stems from oxidation of atmospheric-nitrogen in the flame, whereas the latter originates from oxidation of the

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fuel-nitrogen. Pershing and Wendt34 reported that the fuel-NOx constitutes over 75% of the total NOx emissions in air combustion, a finding in good agreement with the results of Courtemanche and Levendis,35 who reported that fuel-NOx contributed 80% of the total NOx for experiments at various furnace temperatures and equivalence ratios. Fuel-nitrogen in coal is contained predominantly in pyrrole-type groups (50
60%); pyridine and quaternary forms have also been detected. Nitrogen contained in pyridine groups has been reported to be more stable than that in pyrrole groups.36 In the combustion process, fuel-nitrogen evolves during both the devolatilization and the char oxidation phases, the distribution depending on the fuel type, the temperature, and the residence time. In the case of bituminous coals the volatile matter nitrogen is released in tarry compounds, which at high temperatures decay mostly to hydrogen cyanide (HCN) and soot-nitrogen.37 In the case of low rank coals and biomass, light nitrogen species may be directly released from the solid matrix as HCN, ammonia (NH3) and cyanuric acid (HNCO).37 A survey of the many possible reaction paths by which HCN is converted to NO and other products, through an amine radical pool, shows the complexity of the gas-phase chemistry.37,38 Flagan and Seinfeld39 summarized the overall chemistry scheme as follows: fuel-N in tars converts expediently to HCN, proceeding to NHi intermediates, which then either oxidize to NO by reactions with oxidants such as OH or reduce to N2 by reactions with NO. The majority of char-bound nitrogen may leave the surface as NO, which is formed as char nitrogen is oxidized to NO. This is then partially reduced by reactions with CO or char as it traverses the particle pores; unreacted NO escapes from the boundary layer and mixes into the bulk gas. The char nitrogen conversion is complicated, as formation of CN or NH is also possible.39,40 Conversion of the mass of fuel-nitrogen to NOx in experimental systems varies from relatively low levels up to nearly 100%.41 Levy42 reported that the range of conversion of coalbound nitrogen to NOx is wide (15
40%), and called this variability in fuel-nitrogen conversion, and the lack of its clear understanding, a major unresolved issue in fuel-NOx combustion control. This was echoed at a later time by Visona and Stanmore43 and then, again, by Glarborg et al.,37 who remarked that in spite of progress over the last three decades, the basic mechanisms for fuel-nitrogen conversion, are still being clarified, and unresolved issues may limit the potential for effective NOx control. The aforementioned variability also underscores the opportunity for significant reductions in NOx emissions by appropriately controlling the combustion environment. This is especially of interest to combustion staging and, most recently, to oxy-combustion. Laboratory experiments in pulverized coal combustion have shown that the stoichiometry exerts a strong effect on NOx levels and on the distribution of fuel-nitrogen among gaseous products. Pohl and Sarofim44 burned bituminous and lignite coals in air over a wide range of bulk equivalence ratios (ϕ = 0.1
5.5), at a furnace temperature of 1500 K. They reported that the conversion of the fuel-nitrogen to NO decreased with increasing ϕ, from 60% at ϕ = 0.2 to 10% at ϕ > 1.5. They mentioned that at high ϕ's, nitrogen remained in the unreacted chars. In agreement with the above, Courtemanche and Levendis35 reported that, over a range of bulk equivalence ratios (ϕ = 0.5
1.5) and over a range of furnace temperatures (1300
1600 K), the conversion of the nitrogen in a bituminous coal to NOx decreased with increasing ϕ from 40% at ϕ = 0.5 to below 10% at ϕ = 1.5. The effect of furnace gas temperature, in 2851

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Energy & Fuels the aforementioned range, on NOx was found to be significant. However, Kremer and Schulz45 reported the NO emissions from combustion of high volatile bituminous coal to be rather independent of furnace temperature, as did Spinti and Pershing46 for combustion of bituminous coal chars. During pulverized coal combustion, fuel-nitrogen is either released with the volatiles or remains within the char, roughly in proportion to the char yield.39 This is supported by Haussmann and Kruger,41 who found that char nitrogen represents the majority of the original fuel-nitrogen, in the gas temperature range of 1200
1700 K. Upon devolatilization, De Soete,47 and Chen and Niksa48 reported that the fraction of char nitrogen converted into NO during char oxidation is roughly proportional to the degree of char burnout. No evidence was found by Nelson et al.36 that the total fuel-nitrogen released depends on coal rank or coal-nitrogen content, although the fraction of the coalnitrogen released with the volatiles increases with decreasing rank, i.e., increasing oxygen content in the fuel.49 Spinti and Pershing46 detected some influences of the coal rank in the char combustion phase and reported that when chars burned in nitrogen-free oxidant the char-N to NOx conversion was higher for lignites (50
60%) than for bituminous coals (40
50%). In addition to burning bituminous and lignite coals, Pohl and Sarofim44 also burned lignite coal chars over a wide range of bulk equivalence ratios (ϕ = 0.1
5.5), at a furnace temperature of 1500 K. They reported that the conversion of the fuel-nitrogen in the lignite coal chars to NO decreased with increasing ϕ, from 25% at ϕ = 0.2 to 4% at ϕ > 1.5. Thus, by comparison with the aforementioned coal combustion experiments, they concluded that 60
80% of the NOx was contributed by the oxidation of nitrogen released with the volatiles; i.e., the remaining 20
40% NOx was released during char combustion. Pershing and Wendt50 burned both bituminous and lignite coals and their chars at ϕ = 1.15 and also concluded that less than half of the original coal-nitrogen is converted to NOx during the char combustion phase. Levendis51 reported on the roles of volatile matter combustion and char combustion phases of the Pittsburgh #8 bituminous coal on NOx formation at fuel-lean conditions (ϕ = 0.4). This coal released 60 wt % of its fuel-nitrogen during devolatilization, 35 wt % during char combustion, with the remainder (5 wt %) staying with carbon in the ash. However, not all of the released fuel-nitrogen formed NOx. Roughly 42
47% of the coal-nitrogen was converted to NOx, out of which approximately 15% was converted during the volatile and 30% during the char combustion phases. The above is in agreement with the findings of Pohl and Sarofim,44 who also reported ≈40% for coal-nitrogen conversion to NOx for the same coal (Pittsburgh #8) burning under similar fuel-lean combustion conditions (ϕ = 0.5). Increasing the gas temperature, in the limited range 1400
1600 K, mildly increased the total amount of fuel-nitrogen converted to NOx.51 The effects of parameters such as nitrogen content in coal, particle size, surface area of the chars, total pressure, O2 partial pressure in the gas, NO partial pressure in the gas, etc. are briefly discussed in this paragraph. Spinti and Pershing46 reported that the apparent conversion of char-N to NOx decreased as the level of the initial NOx mole fraction in the surrounding gas increased. To the limit, in their study, the char-N to NOx conversion dropped to nearly 0% at a level of 900 ppm NOx in the flame. Chaikalangmuang et al.52 reported that in unstaged burners, the formation of NOx increased with a coal’s volatile matter content, but in staged burners the formation of NOx decreased with

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increasing volatile matter content. Seeker et al.53 reported that small particles produce more fuel-NO than large particles. Aho et al.54 reported that NO formation decreased sharply with reactor pressure, and mildly increased with reactor temperature and oxygen mole fraction; they also provided an empirical formula to estimate the NO mole fraction based on those parameters (yNO % =
11.63 þ 0.04557  T (°C)
2.33  p (bar) þ 15.992  pO2 (bar)). Visona and Stanmore43 reported that increasing the inlet oxygen mole fraction (in the range yO2 = 5
25%) generated more NO. This was corroborated by Spinti and Pershing46 (in the range yO2 = 21
28%) and by Hu et al.55 (in the range yO2 = 20
50%). At higher oxygen mole fractions (yO2 > 50%) NOx emission decreased, and in pure oxygen it even went back to the same level as that in air. Lazaro et al.56 reported that the lower the surface area of the char the higher the fraction of the char-nitrogen that is released as NO (the NO/N ratio). Finally, there has been some research related to the evolution of NOx in CO2-rich atmospheres, as is the case in oxy-fuel combustion.17,23
25,27,55,57
60 Comprehensive reviews on oxyfuel combustion have been published in recent years21,22,61 and have reported on emissions of NOx. In pilot-scale demonstrations on pulverized oxy-coal combustion, reductions in NOx emissions by as much as 65% have been observed.20,22 These drastic NOx reductions may be caused by factors, such as the absence of atmospheric nitrogen, changes in the combustion characteristics of coal, reburning of the recycled exhaust gas, reactions with char, etc.37,42,62 Emissions of Sulfur Dioxide (SO2). Sulfur exists in coal in inorganic forms, predominantly pyrite (FeS2), or in organic forms, such as thiophene, sulfides, and thiols. The sulfur content of coals varies from less than 1 to over 12 wt %.63 In fuel-lean combustion, the majority of this sulfur is typically oxidized to form SO2.29 Courtemanche and Levendis35 examined the emissions from combustion of a pulverized bituminous coal over a range of bulk equivalence ratios (ϕ = 0.5
1.5) and furnace temperatures (1300
1600 K). They reported that the conversion of the sulfur in the coal to SO2 decreased with increasing ϕ, from nearly 100% at ϕ = 0.5 to as low as 40% at ϕ = 1.5. Moreover, a decrease in conversion with increasing furnace gas temperature was noticed. By examining the sulfur content in the parent coal and its char derivatives upon pyrolysis,45,64,65 it was determined that the sulfur that remained in the char was proportional to its mass yield. A few coals, however, were reported to exhibit preferential enriching of the char with sulfur.65 Atal et al.66 and Levendis51 studied the sulfur release during volatile matter combustion and char combustion phases of the Pittsburgh #8 bituminous coal, under fuel-lean conditions. Nearly all the released sulfur (90
95%) was converted to SO2. Small amounts of sulfur remained in the collected ash of this lowcalcium content coal. Approximately 57 wt % of the sulfur content of this coal was released as SO2 during the combustion of volatiles, whereas 33% of the parent coal sulfur was released during the combustion of char. This is contrary to the observation of Wells et al.65 who found that the char was preferentially enriched in sulfur. The difference could possibly be due to the experimental temperatures, heating rates and oxidative conditions. SO2 emissions generally correlate with the sulfur content of the fuels. Thus, the addition of biomass has been shown to reduce SO2 emissions, mainly due to its low sulfur content in most cases67,68 and due to biomass ash composition.61 SO2 emissions have also been correlated with the organic and inorganic sulfur 2852

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Table 1. Chemical Composition of the Coals and the Bagasse Biomassa PSOC-1451 rank and fuel source

DECS-11

bituminous high volatile A,

PSOC-1443

lignite A,

DECS-26

lignite A

Pittsburgh #8

Beulah,

Pennsylvania

North Dakota

sub-bituminous B,

Titus, Texas

River Basin

bagasse sugar cane residue, Brazil

Wyodak, Wyoming

Proximate Analysis As Received (upon Re-Evaluating Moisture) moisture (%)

2.5

33.4 (13.2)

28.5 (18.6)

26.3 (13.1)

4.4

volatile matter (%)

33.6

37.4 (48.6)

44.2 (50.3)

33.1 (39.0)

83.9

fixed carbon (%)

50.6

22.9 (29.8)

12.0 (13.7)

35.1(41.4)

7.7

ash (%)

13.3

6.4 (8.4)

15.3 (17.4)

5.6 (6.5)

4.0

carbon (%)

71.9

66.2

56.8

69.8

44.3

hydrogen (%)

4.7

4.0

4.1

5.7

5.7

oxygen (%) (by diff.)

6.9

18.6

15.8

15.6

45.5

nitrogen (%)

1.4

0.9

1.1

0.9

0.2

sulfur (total) (%)

1.4

0.7

0.7

0.4

0.07

sulfur (pyritic) (%)

0.82

0.31

0.09

0.07

sulfur (organic) (%)

0.53

0.39

0.64

0.35

sodium (%) calcium (%)

0.06 0.28

0.66 1.8

0.04 1.4

0.09 1.1

2.7

ash (%)

13.7

9.6

21.4

7.6

4.2

heating value dry fuel (MJ/kg)

31.5

25.7

23.0

28.2

16.3

Ultimate Analysis (on a Dry Basis)

a

For the four coals, their proximate and ultimate analysis data were obtained from the Penn State Coal Sample Bank; upon opening the sealed containers of the supplied coal samples, variations of moisture content with storage in the laboratory were observed for all, but the bituminous, coals. The measured moisture content values are listed (in parentheses) and the remaining proximate analysis values were re-calculated and are also shown (in parentheses). The specific bagasse sample was analyzed at the University of S~ao Paulo laboratories, S~ao Carlos Campus.

content of fuels; it has been reported that bituminous coals have inorganic sulfur with a loosely bound portion that can be released at a faster rate than the organic sulfur.69 Finally, SO2 emissions have also been reported to inversely correlate with the calcium content of the fuels, as well as to that of other alkaline-earth metals (sodium, potassium, and magnesium). High sulfur retention in the ash has been reported during combustion of subbituminous and lignite coals having calcium content in the ash sufficiently high to result in near-stoichiometric calcium and sulfur amounts.70 Spliethoff and Hein68 showed that the higher the alkaline-earth content in the ash, the more the sulfur retention therein. Raask71 proposed an empirical formula for predicting the sulfate retention, Sr, in the ash: Sr = ((0.7 Na% þ 0.41 K% þ 0.8 Ca% þ 1.32 Mg%)/S%)  (1
0.09 (ash%)2/3).

’ EXPERIMENTAL SETUP AND PROCEDURE Coals from four different ranks were burned in this study, as listed in Table 1. Samples for the four coals were obtained from the Penn State Coal Bank, and were ground and sieved. A size cut of 53
90 μm was used herein. Two of the coals (the PSOC-1451 bituminous and the PSOC-1443 lignite) were extensively characterized in previous research.72 Sugar cane bagasse was collected directly from a mill located in Brazil, S~ao Paulo State. The bagasse was washed, dried at 90 °C for 24 h, chopped in a household blender and sieved. Pictures of the raw bagasse before and after preparation are shown in Figure 1. Bagasse particles were needle-like in shape and proved difficult to fluidize and feed to the furnace through the capillary tubing used to feed the furnace injector (Figure 2). An exception was the case of particle sizes